High-strength black polyurethane foams

ABSTRACT

Black polyurethane foams that exhibit higher strength black colorations without the need for concomitant increases in black colorants therein are provided. Such a resultant jetter black foam article is possible through the unexpectedly effective introduction of small amounts of certain toner compounds or combinations that exhibit specific measurable appearance characteristics. Such toners exhibit at least one absorption peak within a specific range of wavelengths (e.g., from about 560 to 610 nm) and specific ranges of half-height bandwidths (from 40 to 130 nm). Furthermore, such a compound or combination of compounds, is preferably liquid in nature (at room temperature) or in dispersion form and may thus be easily incorporated within target polyurethane precursor compositions for admixture with either black pigments (or dispersions thereof), black polymeric (liquid) colorants, or both. Methods of high strength black polyurethane foam production as well as separate pigmented and liquid polymeric colored foams of such type including the necessary toner compounds and/or combinations, as noted above, are also encompassed within this invention.

FIELD OF THE INVENTION

This invention relates to the black polyurethane foams that exhibithigher strength black colorations without the need for concomitantincreases in black colorants therein. Such a resultant jetter black foamarticle is possible through the unexpectedly effective introduction ofsmall amounts of certain toner compounds or combinations that exhibitspecific measurable appearance characteristics. Such toners exhibit atleast one absorption peak within a specific range of wavelengths (e.g.,from about 560 to 610 nm) and specific ranges of half-height bandwidths(from 40 to 130 nm). Furthermore, such a compound or combination ofcompounds, is preferably liquid in nature (at room temperature) or indispersion form and may thus be easily incorporated within targetpolyurethane precursor compositions for admixture with either blackpigments (or dispersions thereof), black polymeric (liquid) colorants,or both. Methods of high strength black polyurethane foam production aswell as separate pigmented and liquid polymeric colored foams of suchtype including the necessary toner compounds and/or combinations, asnoted above, are also encompassed within this invention.

BACKGROUND OF THE PRIOR ART

Black polyurethane slabstock foams [e.g., foam colors when substantiallyall of the light in the visible electromagnetic spectrum (400–700nanometer) is absorbed] are utilized in a variety of articles,including, without limitation, high fidelity speakers, earphones, andthe like. Such black colorations are generally provided through pigmentsor pigment mixtures or through polymeric colorant mixtures (of variouscolors, such as mixtures of blue, yellow, red colorants). Black colorantcompositions may be individual pigments or mixtures with other pigments(particularly other black pigments) or mixtures of two, three or moreindividual polymeric colorants. Such mixtures generally complement eachother to absorb light across the visible spectrum. For example, orangeand blue; yellow, red and blue; and orange, blue and purple representcolor combinations which will create a black composition. In general, ablack colorant composition of one or more black pigments or combinationsof two or more dyes or polymeric colorants will absorb electromagneticradiation across the entire visible spectrum, but the absorbance at eachwavelength may not be uniform. Consequently, the absorbance of such acomposition may be represented by a series of peaks and valleys acrossthe visible spectrum such that any loss or modification of any of thecomponent absorbance levels may result in the change of jetness or eventhe hue of the target black coloration.

Polymeric colorants have become the preferred coloration method inindustry for colored polyurethane products, such as foams, resins, andthe like. Being liquid in nature, these polymeric colorants containhydroxyl terminated polyoxyalkylene chain (or chains) and actually tendto react to and within the urethane during polymerization. As a result,the color is integrated within the foam and provides excellentuniformity and depth throughout the entire article. Generally, thesecolorations are performed in situ during foam, resin, etc., formation.For instance, polymeric colorants (i.e., polyoxyalkylenated colorants),such as those described in U.S. Pat. No. 4,284,279 to Cross et al., havebeen introduced within polyol compositions during slabstock foamproduction. The “colored” polyol then reacts with an isocyanatecomposition to form the desired colored foam. Such foamed productsrequire the presence of a catalyst or catalysts to effectuate thedesired reaction between the polyol and isocyanate components.

Potential jetness shifts may be caused by improper mixing of componentcolorants, uneven lighting for viewing, light exposure (and thus, forexample, UV degradation of components), and the like. In essence, deep,dark, jet-black shades are generally difficult to provide within suchpolyurethane foam articles due to the potential for the individualshades (yellow and/or red) either to absorb insufficiently or in excessat maximum wavelengths to the extent that imbalanced absorption by theindividual coloring components therein may, in effect, impart a limitedjetness appearance (through increased yellowness, redness, or both).

As for black pigments, the colorations are mostly provided by singlesources (unless mixtures of different black pigments are present).However, such coloring agents appear to exhibit a limit to color depth,most likely due to the absorption levels inherently provided by theindividual pigments themselves. A broad absorption peak, such as thattypically exhibited by such pigment materials, imparts a limited jetnesseffect within certain target articles, most notably here, for blackpolyurethane slabstock foams. The limited jet-black appearance is mostlikely the result of certain wavelengths within the absorption spectrumof the specific pigment particles either being “masked” or impeded fromview or being too prevalent for perception by the naked eye. The resultis a perceived color that is, generally, too yellow or red to impart adeep, dark color within the target black foam. As a result, theresultant yellowing or reddening of the black color compromises thedesired jetness thereof, thereby rendering a black coloration exhibitinga limited jetness appearance (empirically).

Therefore, as discussed and/or alluded to above, such black colorations(provided by either pigments or polymeric colorants) typically sufferfrom a lack of strength, particularly in terms of presence of limitedamounts of coloring agents therein, to the extent that the depth ofblack colorations within the target foam is aesthetically lacking due tosuch limited jetness appearance. Improvements have been attempted, mostnotably through increases in the amount of pigment (carbon black, forexample) or polymeric black colorant (REACTINT® X77, from Milliken &Company, for example) added; however, in such a manner, the cost ofproduction increases while the relative improvement in color strength isnot proportionally better. Such a disparate result thus has led to areturn to certain lower levels of pigment or polymeric colorant utilizedwith the same aesthetically displeasing low-color-strength black resultsprevalent.

Also, due to the limitation of the existing state of the art dispersiontechnology, the amount of pigment (carbon black, for example) can bedispersed into liquid media is limited due to extremely high viscosity.Current commercial carbon black dispersions are thus limited in colorstrength (e.g., the L* value) even with maximum loadings of pigmentdispersions or a mixture of polymeric colorants within target foamswithout affecting ultimate polyurethane foam performance primarily dueto high unwanted yellowness and, possibly, redness, levels measuredwithin those previously made black polyurethane foams.

Improvements within the aforementioned polymeric colorant mixtures areas difficult to provide, primarily since the determination of properlevels of each component color can be altered when greater amounts ofthe total black colorant are introduced within target slabstock foams.Thus, modifications in flairing appearance, or, at least, in the rednessand/or yellowness, thereof, are quite possible, such that the desiredhigh-color-strength black foam is difficult to achieve. A simplifiedprocedure and/or formulation to provide such desired high color strengthresults is thus necessary; unfortunately, to date, such a formulationhas not been provided the black polyurethane slabstock foam industry.

DESCRIPTION OF THE INVENTION

It is therefore an object of this invention to provide a novel blackcolorant composition for the coloration of polyurethane articles thatincludes at least one toner compound. It is a further object of thisinvention to provide a novel black colorant composition, comprisingeither polymeric colorants, pigments, or both, that imparts a jetnesslevel within polyurethane slabstock foam above that for either polymericcolorants or pigments alone. A further objective is to provide a blackcoloration method for polyurethane production that effectively reducesand/or eliminates color dullness, degradation, and/or shift of hue whichin turn improves the perceived jetness thereof, through the presence ofa toner compound therein. An additional object of the invention is toprovide a single compound or a combination of colorants as a toning(e.g., bluing) agent for black-colored polyurethanes, preferably, thoughnot necessarily, black-colored polyurethane slabstock foams.Additionally, it is an object of this invention to provide a polyol orisocyanate composition comprising a toner compound as a precursorcomposition for the manufacture of polyurethanes.

Accordingly, this invention is directed to a black-colored polyurethanearticle comprising at least one black coloring agent, selected from thegroup of at least one pigment, at least one combination of polymericcolorants that impart a black coloration to said polyurethane, and anymixtures or combinations thereof, and at least one toner compound thatimparts darkening effects within said article; wherein, optionally, saidat least one toner compound exhibits at least one absorption peak and aλ_(max) between 560 and 610 nm within said polyurethane article; andwherein said at least one toner compound exhibits a specific half-heightbandwidth range of between 40 and 130 nm in relation to said at leastone absorption peak; and, further optionally, wherein said at least onetoner compound is a combination of compounds that comprises a firstcompound exhibiting a single absorption peak and a λ_(max) between 560and 575 nm and a second compound exhibiting a single absorption peak anda λ_(max) between 576 and 610 nm. Furthermore, this inventionencompasses a liquid solution or dispersion comprising either at leastone polyol or at least isocyanate, at least one coloring agent asdefined above, and at least one toner compound as defined above,wherein, optionally, said at least one toner compound exhibits the sameabsorption characteristics as listed above.

Also encompassed within this invention is a method of producing a blackpolyurethane article comprising the steps of: a) providing a polyolcomposition; b) providing an isocyanate composition; wherein at leastone of the compositions of steps “a” and “b” comprises a black colorantformulation comprising at least one toner compound or combination ofcompounds; and c) reacting all of the compositions from steps “a” and“b” together in the presence of a suitable catalyst to produce apolyurethane article. A polyurethane article, preferably though notnecessarily a foam article, produced by these methods and/or exhibitinga substantially uniform black coloration throughout is also contemplatedwithin this invention.

In general, polyurethane foam is produced through the catalyzedpolymerization of the reaction products of polyols and isocyanates. Sucha reaction is well known throughout the polyurethane industry and hasbeen practiced for many years. The potential number and types of polyolsutilized within this invention are plentiful. Such a compound is definedas comprising at least two alcohol moieties, preferably at least three.The free hydroxyl groups react well with the isocyanates to form theurethane components which are then polymerized to form the desiredpolyurethanes. Blowing agents present within the polymerization stepprovide the necessary foam-making capability. Preferred polyols thuscomprise between three and six alcohol moieties, comprising from betweenone and six carbon atoms per alcohol moiety. Most preferred is a typicaltrifunctional polyol, such as F3022 polyol, available from Bayer.

Isocyanates, most preferred diisocyanates, are well known components ofsuch polyurethane foams and include any compounds which possess at leastone free cyanate reactive group, and most preferably two, although moremay be utilized. Such compounds may also be aliphatic or aromatic innature. The most prominently utilized isocyanates, and thus the mostpreferred types for this invention (though not required), are toluenediisocyanate (TDI), diphenylmethane diisocyanate (MDI)(aka, methylenediisocyanate)(others, such as aliphatic isocyanates may be utilized, aswell as other aromatic types). The polyol is generally reacted with aslight excess of isocyanate (ratio of from 1:0.85 to 1:1.25) to producea soft flexible foam product; the greater the ratio, the harder theproduced foam). For rigid foams the excess isocyanate index issubstantially higher (1:2.0 to 1:4.0). In practice, two separate streamsof liquids (one of polyol, the other of isocyanate) are mixed togetherin the presence of a polymerization catalyst and a blowing agent inorder to produce the desired polyurethane foam product. As noted above,this invention is directed to polyurethanes in general, with foamarticles most preferred. Laminates, solid articles, and any other typeof colored polyurethane, are also encompassed within this invention.

The term “tertiary amine-based catalyst” is intended to encompass anyreactive amine catalysts including the gelation/blowing catalystsutilized within polyurethane production which comprises at least oneamine constituent. As noted above, amine-based catalysts, and morespecifically, tertiary amine catalysts, are widely utilized within suchspecific foam-producing methods. Two catalysts, in particular, DABCO 33LV and DMEA, are excellent gelation/blowing catalysts for this purpose.The amount of tertiary amine catalyst required to effectuate the desiredurethane polymerization is extremely low, from between 0.05 php to about1.00 php of the entire foam-making composition.

The term “black coloring agent” is intended to encompass any pigment,pigment dispersion, polymeric colorant, dye, dyestuff, any mixturesthereof, and the like, which provides desirable black colorations totarget polyurethane foam articles. In general, such black coloringagents are added to the polyol stream (prior to reaction with theisocyanate) in amounts ranging from about 0.001 php to about 10 php.Higher color loadings are economically unacceptable, not to mention theymay cause certain migratory, crocking, and/or bleeding problems.Suitable black pigments for this invention include, without limitation,carbon black, lamp black, and the like, including such pigments that areadmixed with certain viscosity modifying agents (propylene carbonate,butyrolactone, and the like), such as those disclosed within PCTPublication Nos. WO/01/94474 and 94484, both to Xia et al. Suitableblack polymeric colorants for this purpose are disclosed within U.S.Pat. No. 5,731,398 to Ragsdale et al., again without any limitation, andas merely examples.

Other additives or solvents may also be present within the foam-makingcomposition. Auxiliary blowing agents are required to provide thenecessary foam blowing capability and reduce chances of combustion. Suchcompounds include methylene chloride, acetone, carbon dioxide (which maybe liberated during the reaction between water and isocyanate), and thelike, and are present in amounts of between about 1.0 php and 10 php ofthe entire foam-making composition. Water may thus also be added inrelatively low amount (i.e., from about 1.5 to about 10 php; mostpreferably between about 3 and 5.5 php) to provide carbon dioxide forblowing purposes. Silicones may be added to provide desired cellstructure and foam stability and are present in an amount from about 0.1to about 2 php of the entire foam-making composition; preferably fromabout 0.5 to about 1.6 php.

Toners have been utilized within certain resins in the past, mostimportantly for the purpose of preventing or neutralizing yellowingwithin transparent types, such as polyester. However, no such type ofcompound has been disclosed or fairly suggested as a proper additivewithin polyurethanes, and specifically, within black polyurethanes, suchas, as one example, slabstock foams. Certain writing and/or printinginks have included bluing agents for toning purposes; however, suchformulations are uniform in appearance and are generally easy to tone insuch a manner for that reason. Foams, by rule, are comprised ofindividual cells of polyurethane that potentially exhibit differingappearances on an individual level. Thus, toning has not been undertakenwithin such articles in the past.

Such toners (being pigments or polymeric colorant types themselves)should exhibit at least acceptable stability when exposed to the light,humidity, temperature, and other such drastic conditions associated withpolyurethane foam manufacturing. Such bluing agents should also exhibita minimal degree of thermal degradation (or, conversely, excellentthermal stability) during polyurethane production, desirably at anystage during production, but acceptably at any stage of the articlemanufacturing process.

For the purposes of this invention, the term “bluing agent” issynonymous with “toner compound”. Such a term thus encompasses either asingle compound or a combination of compounds that combats andneutralizes the yellowing, reddening, or both, of the target blackpolyurethane article, which, in turn, imparts a darker and jetter blackappearance within target black-colored polyurethane foam articles. Asnoted above, such yellowing and, possibly, reddening have beendetermined to provide limited jetness effects to target blackpolyurethane articles, most notably, though not limited to, blackpolyurethane slabstock foam articles, thereby creating aestheticproblems therein. The inventive toner for this purpose foundunexpectedly provides a bluing effect (e.g., decreasing b* values) thatabsorbs within the needed wavelength range complementary to any yellow(and possibly red) coloration therein (at least one toner exhibiting aλ_(max) from 560 nm to 610 nm; more preferably from 565 to 600 nm; mostpreferably from about 570–595 nm), particularly with a half-heightbandwidth within the range from about 40 to 130. Such a toner (bluingagent) thus imparts a darkening effect to the target black coloredpolyurethane foam by combating yellowing and possibly (though notnecessarily) by combating reddening to the extent that such a foamarticle exhibits an L* value corresponding to a black color strengthcomparable at least to the approximate level achieved by an articlecolored with the same black coloring agent but without any tonerpresent. Thus, in every instance an inventive toner additive is presentthe b* value is decreased (thus indicating an increase in the bluenessand thus a reduction in yellowness) in comparison with the samenon-toned black sample (but comprising either the same or a lower amountof black coloring agent than the non-toned article). In some situations,and thus with certain toner additives, the redness, or a* value, of thetarget black foam is reduced as well in comparison with the same type ofnon-toned black foam sample. Furthermore, the L* value may also bereduced for the target black foam sample upon introduction of a toneradditive within the manufacturing (polymerization and coloring) processas well (although an L* value reduction in comparison with a non-tonedsample is, again, not necessary to achieve the desired jetnessimprovements mentioned above).

In addition, it was determined that such a variable as absorption wasnot the only necessary toner (bluing agent) property required to providethe best overall bluing characteristics to darken the black effect(jetness) within the target polyurethane foam with a lower amount ofblack colorant required to attain such dark levels. Thus, a single peakor narrow multiple peaks exhibited by such a toner (or toners)facilitates addition and control of the needed final jetness result. Ofequal importance was determined that a single absorption peak required aspecific half-height bandwidth range for a number of reasons. Mostimportantly, such a specific half-height bandwidth range has been foundto impart a significant dark result in the target polyurethane article,and thus an increase in overall jetness of the black foam (through, asnoted above, what is believed to be a reduction in yellowing, reddening,and/or other discolorations that effect the perceived jetness thereof).Most standard bluing agents for typical writing and/or printing inks,polyesters, and other types of non-polyurethane-based articles tend toprovide excellent neutralization of yellowness within target media;however, generally, and particularly within certain end-use articles,such as printing inks and clear or transparent thermoplastics, thehalf-height bandwidths of such additives are so broad that absorptionvalues are extensive over a broader range of wavelengths to the extentthat such toners not only effectively neutralize the yellowness, butalso dull the finished drawn-down ink or finished plastic article.Although this invention includes, in its broadest scope, the presence ofany bluing agents for toning of the target black polyurethane articlesherein, it has been found that optimum effects are provided through theinventive addition of such specific toners as noted above. Inparticular, the limited jetness appearance imparted by addition ofpigments alone has been remedied unexpectedly through the utilization oftoners first, and more pointedly and successfully, through addition ofthe narrow half-height bandwidth types noted above. However, it is alsoforeseen that too narrow a half-height bandwidth may produce unwanteddifferent colors (such as, for example, green colorations) within thefinished article due to a potential lack of proper complementaryabsorption capabilities from a broad enough perspective to combatredness and/or yellowness completely. The specific limit on narrownessin such a situation is not known, however, although, again, it isforeseen that a limit to the effectiveness upon too narrow a measurementdoes exist.

Black colorations within polyurethane foams are accorded with any numberof different coloring agents. Most prominently used are polymericcolorant combinations (as noted above), such as REACTINT® Black X77(from Milliken & Company) or pigments, such as carbon black, lamp black,and the like. Such pigment coloring agents may be present either insolid, powder form or in dispersion form (for ease in handling andintroduction), such as a mixture of 90% by weight of carbon blackdispersion (in particular, UNION BLACK™ 3U-600 from Union Chemical) and10% by weight of propylene carbonate, RYVEC Black DR 2100 (from Ryvec),REBUS Black 2106, and REBUS Black 2125 (both from Rebus). Many otherblack coloring agents useful within this invention, particularly similarblack pigments and pigment mixtures to those above.

Such a toner compound can be added in the amount from about 0.1 to about15% (with from about 0.05 to about 7.5% of each individual componentwithin the inventive combination permitted; preferably from about 0.5 toabout 6% each; more preferably from about 1 to about 5% each; and mostpreferably from about 1.5 to about 4.5% each) of the total parts ofblack coloring agent present within (aka, added to) the targetpolyurethane foam. The level of loadings depends highly upon thestrength of the colorant needed to provide the desired anti-yellowing,-reddening, -jetness limiting, etc., effect while also not contributingan excess in blue or violet discoloration to the target polyurethane.The class of compounds that exhibits such effective and beneficialcombined characteristics includes those within the noted range of narrowwavelengths above. Thus, a violet or bluish-violet colorant exhibitingan absorption maximum of between about 560 to 610 nm is preferred forsuch purpose. The class of individual compounds that exhibit sucheffective and beneficial characteristics include violet and violetbluish colorants (noted from the absorption spectrum range above),potentially preferred to be liquid or pigment dispersion; most preferredbut not necessarily liquid in nature, and include a chromophore withpoly(oxyalkylene) pendant chains thereon of at least 2 moles ofoxyalkylene per alcohol chain. Such colorants are generally referred toas polymeric colorants, disclosed on a general basis within numerouspatents assigned to Milliken & Company, and marketed by the samecorporation under the tradenames REACTINT® and LIQUITONE®, as examples.Preferred are polymeric violet blue colorants that exhibit a λ_(max)within the proper range of wavelengths (i.e., preferably between 560 and610 nm). Such colorants should also preferably exhibit a single peakwithin this range as well as a half height bandwidth of from about 40 toabout 130 nm, more preferably at most 120 nm, still more preferably fromabout 50 to 115 nm, and most preferably from about 60 to about 110 nm,all in order to provide the best overall anti-yellowing capabilitieswith provision of high jetness levels within target black polyurethanefoams. The more preferred colorant types are violet blue colorantshaving triphenylmethane- or thiophene-based chromophores and polymericchains thereby making the colorants liquid at room temperature and in anon-diluted, pure state. The most preferred types are selected fromthose conforming with the structures of Formulae (I) or (II), allproviding either blue or violet shades (all uses of the word alkyl oralkylene throughout is intended to mean from 1 to 18 carbons, unlessotherwise noted):

wherein R₁, R₂, and R₃ are the same or different and independentlyselected from the group consisting of hydrogen, hydroxyl, straightC₁–C₂₀ alkyl, C₁–C₂₀ alkoxy, cyano, sulfonyl, nitro, phenyl, substitutedphenyl, cycloalkyl, carboxyl, amido, and branched C₁–C₂₀ alkyl groups; Rand R₄ are the same or different and are selected from the groupconsisting of hydrogen, hydroxyl, straight and branched C₁–C₂₀ alkyl,C₁–C₂₀ alkoxy groups; R₅ and R₆ are the same or different and areselected from the group consisting of hydrogen, C₁–C₂₀ alkyl, C₁–C₂₀alkoxy, phenyl and substituted phenyl, and [polyoxyalkyleneconstituent]_(z)R′, wherein z is from 1 to 20 (indicating an averagenumber of moles of oxyalkylene present, and thus is not required to bean integer); polyoxyalkylene constituent is selected from the groupconsisting of at least one monomer selected from the group consisting ofat least one C₂–C₂₀ alkyleneoxy group, glycidyl, or mixtures thereof;and R′ is selected from the group consisting of hydrogen, C₁–C₂₀ alkyl,C₁–C₂₀ alkylester, halo, hydroxy, thio, cyano, sulfonyl, sulfo, sulfato,aryl, nitro, carboxyl, C₁–C₂₀ alkoxyl, amino, alkylamino, acrylamino,C₁–C₂₀ alkylthio, alkylsulfonyl, C₁–C₂₀ alkoxylcarbonyl and phenylthio.Most preferably groups R₅ and R₆ represent, hydroxyl-terminated C₁–C₈poly(oxyalkylene) groups (including monomers such as, preferably,ethylene oxide, propylene oxide, and any combinations thereof).

wherein R₅ and R₆ are as defined above; R₇, R₈, R₉ and R₁₀ are the sameor different and are selected from the group consisting of hydrogen,C₁–C₂₀ alkyl, C₁–C₂₀ alkoxy, phenyl and substituted phenyl, and[polyoxyalkylene constituent]_(z)R′, within z is from 1 to 20(indicating an average number of moles of oxyalkylene present, and thusis not required to be an integer); polyoxyalkylene constituent isselected from the group consisting of at least one monomer of at leastone C₂–C₂₀ alkyleneoxy group, glyccidyl, or mixtures thereof; and R′ isselected from the group consisting of hydrogen, C₁–C₂₀ alkyl, C₁–C₂₀alkylester, halo, hydroxy, thio, cyano, sulfonyl, sulfo, sulfato, aryl,nitro, carboxyl, C₁–C₂₀ alkoxyl, amino, alkylamino, acrylamino, C₁–C₂₀alkylthio, alkylsulfonyl, C₁–C₂₀ alkoxylcarbonyl and phenylthio; whereinX is selected from the group consisting of F, Cl , Br, I, NO₂, SO₄,HSO₄, PO₄, HPO₄, H₂PO₄, and R″SO₃ (wherein each anion is present in thecorrect number to correspond to the valence number of the cation withinthe colorant itself); and wherein R″ is C₁–C₂₀ alkyl, or phenyl, orsubstituted phenyl.

The ratios in the following table regarding such polyoxyalkylene groupsthus indicate the following: ethylene oxide (EO)/propylene oxide(PO)/ethylene oxide (EO) (if the third number is present, another groupof EO is present; if not then only one group of EO capped with PO ispresent). The following table (Table 1) further shows the most preferredtypes, and #1 (having a Color Value of 24 abs/g/l, when diluted withFOMREZ® 11-225, a polyester/polyol from Crompton Corporation, and a halfheight band width of 98 nm) and #5 (having a Color Value of 60 abs/g/lin its undiluted state, and a half height bandwidth of 78 nm) are thepreferred embodiments (the numbers for R₅/R₆, R₇/R₈ and R₉/R₁₀ below arethe sums of both groups, for example 2/15/5 indicates 1 mole of EO, 7.5moles of PO, and 2.5 moles of EO per group; and 5/5 indicates 2.5 molesof EO, and 2.5 moles of PO per group):

TABLE 1 Toner # Formula R₁/R₃ R₂ R₄/R R₅/R₆ R₇/R₈ R₉/R₁₀ X λmax Color 1I CN/CN Me Me/H 2/14/8 — — — 573 nm Violet 2 I CN/CN Me Me/H 2/10/8 — —— 573 nm Violet 3 I CN/CN Me H/H 2/7/6 — — — 566 nm Violet 4 I CN/CN MeMeO/MeO 2/10/6 — — — 594 nm Blue 5 II — — — 5/5 Me/Me 5/5 ½ SO₄ 590 nmBlue 6 II — — — 2/15/5 Me/Me 2/15/5 ½ SO₄ 590 nm Blue 7 II — — — 2/10/6Me/Me 2/10/6 Cl 590 nm Blue 8 II — — — 5/5 5/5 5/5 ½ SO₄ 592 nm BlueThese polymeric colorants have found utility in the past as individualcoloring agents for polyurethanes and as fugitive tints for textiles(the end-use dependent on the degree of polyoxyalkylenation of the basechromophore), as taught within U.S. Pat. Nos. 4,507,407 and 4,601,725.However, such colorants have not been taught or fairly suggested asproper bluing agents for improving jetness within any polyurethane foamarticles. As noted above, it was now determined within the scope of thisinvention that proper toner compounds for such black polyurethane foamsnecessarily exhibited certain absorption wavelength ranges and narrowhalf height bandwidths in order to provide the best overall jetnesscharacteristics within target black polyurethanes. The most preferredinventive individual bluing agent, Example toner #5, above, when presentwithin black polyurethane foams at a loading of about 2000–3000 ppm (forexample, in a 2 php black foam, the toning compound presented at a levelof 10–15% of the total black colorant, a sufficient amount to provideactual violet bluish colorations within a otherwise uncoloredpolyurethane foams), and thus at a level well above that needed foreffective toning purposes but at a level at which proper colorimetricmeasurements may be taken in order to predict, on a broader scale,proper toning agents without first using low loadings in the targetpolyurethane foam, imparts excellent toning properties to such targetblack foam articles. Such measurements as follows are thus intended toprovide distinguishing features of the most preferred colorant forutilization as the desired black polyurethane toner. The individualtoner compounds therefore exhibit a λ_(max) of about 590 nm, and ahalf-height bandwidth of about 78 nm. Such a compound, as noted ingreater detail below, thus provides excellent toning (darkening) resultswithin desired black polyurethane articles. Furthermore, being a liquid,such a toner also can be added easily to any stage of the polyurethanemanufacturing process, and can be stored conveniently within a solutionor dispersion with either a polyol or an isocyanate for simultaneous andeffective introduction within such a manufacturing procedure. As such,this toning agent, being merely one example of the potentially workableclass of such colorants, meets all of the necessary requirements notedabove.

Further possible toner compounds for black polyurethane foams includeblue pigments and/or dyes. The most preferred types are selected fromthose conforming with the structures of Formulae (III) or (IV), allproviding blue shade:

wherein M is any metal such as Na, K, Li, Mg, Ca, Cu, Fe, and the like(wherein each cation is present in a number that corresponds the valenceof the anionic species); R₁₁, R₁₂ and R₁₃ are the same or different andare selected from the group consisting of hydrogen, C₁–C₂₀ alkyl, phenyland substituted phenyl; and R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, R₂₁, R₂₂,R₂₃, R₂₄, R₂₅, R₂₆, R₂₇, R₂₈, R₂₉, R₃₀, R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆,and R₃₇ are the same or different and are selected from the groupconsisting of hydrogen, C₁–C₂₀ alkyl, C₁–C₂₀ alkoxyl, halo, hydroxy,thio, cyano, sulfonyl, sulfo, aryl, nitro, carboxyl, amino, alkylamino,arylamino, alkylsulfonyl, alkoxycarbonyl, alkylthio and arylthio; andwherein one of R₂₈, R₂₉, R₃₀, R₃₁, and R₃₂ is a SO₃ ⁻ anion, and alsoone of R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, and R₃₇ is a SO₃ ⁻ anion. The mostpreferred types include, but are not limited to, the reddish shade CIPigment Blue 18 (Formula IV, in which M=Na; R₁₁, R₁₂, R₁₃, R₁₈, R₁₉,R₂₀, R₂₁, and R₂₂=H; one of R₂₈, R₂₉, R₃₀, R₃₁, and R₃₂ is SO₃ ⁻, therest are H; one of R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, and R₃₇ is SO₃ ⁻, and therest are H), greenish shade CI Pigment 56 (Formula III, in which R₁₁,R₁₂, R₁₃, R₁₄, R₁₆, R₁₇, R₁₈, R₂₀, R₂₁, R₂₂, R₂₃, R₂₅, R₂₆, and R₂₇=H;R₁₅, R₁₉ and R₂₄=Me), and mid shade CI Pigment 61 (Formula III, in whichR₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, R₂₁, R₂₂, R₂₃, R₂₄,R₂₅, R₂₆, and R₂₇=H). Furthermore, the most preferred toners forpolyurethane blacks are liquid dispersions containing these pigments,such as ALKALI BLUE™ Flush series of products (available from BASF). AndALKALI BLUE™ FB4365-AB (available from BASF, having a λ_(max) 593 nm inMeOH, and a half height bandwidth of 100 nm) is the preferredembodiment. Such a composition accords similar complementary absorptionspectra to red and yellow colorations to provide the ability to combatsuch limited jetness possibilities as noted above.

Resultant black polyurethane foams may be produced through reaction ofany black pigment or polymeric colorant combination with such toningcompounds. To that end, mixtures of previously prepared pigment/tonermixtures (such as dispersions, and the like) may be admixed with otherpigments (alone) or other pigment/toner mixtures, either beforeintroduction within a polyol or isocyanate stream, or simultaneouslywithin any such stream, or simultaneously or sequentially within apolyol/isocyanate admixture during polymerization. Also, the toner maybe added separately from the pigment(s) during polyurethane productionas well. The same is possible for any number of polymeric colorantcombination/toner mixtures or polymeric colorant combinations admixedseparately with toner(s) during polyurethane polymerization.

Further criteria which the particular inventive individual toner orcombination toners exhibit includes thermal stability while undergo hightemperatures during the polymerization process; no degradation of thepolyurethane either during processing or once the final product is made;cost effectiveness so as not to translate into higher prices for theconsumer; acceptable viscosity in order to permit better processingconditions; homogeneity of dissolution of the toner within the blackpolyurethane; and substantially no migration of the toner from andwithin the resultant black polyurethane foam product. The inventivetoner compounds exhibit all of these necessary characteristics that thusshows the care and degree and analysis required in order to select theproper toner for introduction within the proper black polyurethanearticle.

The black polyurethane article comprises about 0.01 to about 20% byweight of black coloring agent. Preferably the amount of black coloringagent (either pigment or polymeric colorant combinations) is from about0.05 to about 10% and most preferably from about 0.1 to about 8%.Optional additives may include plasticizers, such as dibutyl phthalate,and the like, antistatic agents, stabilizers, antioxidants,antimicrobial, and other similar standard polyurethane additives.

The inventive polymeric toners or liquid dispersions of toner (aka,bluing agent) plus coloring agent plus polyol or isocyanate may includea ratio by parts of polyol to isocynate of from 3:3 to 7:3, with 4:3preferred for flexible foams, and the colorant present in an amount offrom 0.1 to 15% by weight of the total amount of the polyol andisocyanate, and the toner present in an amount from 0.1 to 15% of thetotal amount of colorant(s) present. Preferably, the colorant is presentfrom 0.2 to 10% of the polyol/isocyanate, and most preferably from 0.5to 8. The toner is preferably present in an amount from 2–10% by weightof the colorant, and most preferably from 3 to 8%.

Preferred Embodiments of the Invention

Examples of particularly preferred black polyurethanes are below.Initially, commercially available black colorants (both pigments andpolymeric colorant mixtures) were first compared for color strengthanalyses versus inventive dispersions of pigments/polymeric colorantmixtures with toner compounds. The following table indicates both theinventive and comparative combinations of black colorants (all presentin an amount of 2 php of the eventual polyurethane foam, unlessotherwise noted; the blends of Examples 51–92 and Comparative Examples99–112 were 50/50 mixtures of the noted pigment and/or polymericcolorants in the additive amounts as respectively noted) tested for thispurpose (with the inventive toners and commercially available typeswithout any toners)(note that PC Black, below, indicates the 90% byweight of UNION Black Paste 3U-600 with 10% by weight of propylenecarbonate dispersion noted above, and ALKALI BLUE™ indicates ALKALIBLUE™ FB4365-AB from BASF):

TABLE 2 Inventive and Comparative Black Colorant Additives Ex. # BlackColorant Component (% by weight) 12 PC Black #1 from Table 1 (2%) 13 ″#1 from Table 1 (5%) 14 ″ #1 from Table 1 (7%) 15 ″ #1 from Table 1(10%) 16 ″ #1 from Table 1 (20%) 17 REBUS Black 2106 #1 from Table 1(2%) 18 ″ #1 from Table 1 (5%) 19 ″ #1 from Table 1 (7%) 20 ″ #1 fromTable 1 (10%) 21 ″ #1 from Table 1 (20%) 22 REBUS Black 2125 #1 fromTable 1 (2%) 23 ″ #1 from Table 1 (5%) 24 ″ #1 from Table 1 (7%) 25 ″ #1from Table 1 (10%) 26 ″ #1 from Table 1 (20%) 27 RYVEC DR2100 #1 fromTable 1 (2%) 28 ″ #1 from Table 1 (5%) 29 ″ #1 from Table 1 (7%) 30 ″ #1from Table 1 (10%) 31 ″ #1 from Table 1 (20%) 32 RYVEC DR2100 ALKALIBLUE (2%) 33 ″ ALKALI BLUE (5%) 34 ″ ALKALI BLUE (7%) 35 ″ ALKALI BLUE(10%) 36 PC Black #5 from Table 1 (2%) 37 ″ #5 from Table 1 (5%) 38 ″ #5from Table 1 (7%) 39 ″ #5 from Table 1 (10%) 40 RYVEC DR2100 #5 fromTable 1 (2%) 41 ″ #5 from Table 1 (5%) 42 ″ #5 from Table 1 (7%) 43 ″ #5from Table 1 (10%) 44 REACTINT ® X77 #5 from Table 1 (2%) 45 ″ #5 fromTable 1 (5%) 46 ″ #5 from Table 1 (7%) 47 ″ #5 from Table 1 (10%) 48 0.1php blend of REACTINT ® #5 from Table 1 (7%)¹ X77/RYVEC DR2100 49 0.5php of same blend ″ 50   1 php of same blend ″ 51   2 php of same blend″ 52   4 php of same blend ″ 53   6 php of same blend ″ 54  10 php ofsame blend ″ 55 0.1 php blend of REACTINT ® #5 from Table 1 (7%)²X77/RYVEC DR2100 56 0.5 php of same blend ″ 57   1 php of same blend ″58   2 php of same blend ″ 59   4 php of same blend ″ 60   6 php of sameblend ″ 61  10 php of same blend ″ 62 0.1 php blend of REACTINT ® #5from Table 1 (7%)³ X77/RYVEC DR2100 63 0.5 php of same blend ″ 64   1php of same blend ″ 65   2 php of same blend ″ 66   4 php of same blend″ 67   6 php of same blend ″ 68  10 php of same blend ″ 69 0.1 php blendof REACTINT ® #5 from Table 1 (7%)⁴ X77/PC Black 70 0.5 php of sameblend ″ 71   1 php of same blend ″ 72   2 php of same blend ″ 73   4 phpof same blend ″ 74   6 php of same blend ″ 75  10 php of same blend ″ 760.1 php blend of REACTINT ® #5 from Table 1 (7%)⁵ X77/PC Black 77 0.5php of same blend ″ 78   1 php of same blend ″ 79   2 php of same blend″ 80   4 php of same blend ″ 81   6 php of same blend ″ 82  10 php ofsame blend ″ 83 0.1 php blend of REACTINT ® #5 from Table 1 (7%)⁶ X77/PCBlack 84 0.5 php of same blend ″ 85   1 php of same blend ″ 86   2 phpof same blend ″ 87   4 php of same blend ″ 88   6 php of same blend ″ 89 10 php of same blend ″ (Comparatives) 100 RYVEC Black DR2100 None 101REACTINT ® Black X77 None 102 REBUS Black 2106 None 103 REBUS Black 2125None 104 PC Black None 105 0.1 php blend of REACTINT ® None X77/RYVECDR2100 106 0.5 php of same blend None 107   1 php of same blend None 108  2 php of same blend None 109   4 php of same blend None 110   6 php ofsame blend None 111  10 php of same blend None 112 0.1 php blend ofREACTINT ® None X77/PC Black 113 0.5 php of same blend None 114   1 phpof same blend None 115   2 php of same blend None 116   4 php of sameblend None 117   6 php of same blend None 118  10 php of same blend None¹The toner was present as 7% of the RYVEC pigment additive formulation²The toner was present as 7% of the REACTINT ® polymeric colorantcombination ³The toner was present as 7% of both the RYVEC pigment andthe REACTINT ® polymeric colorant combination prior to admixture of bothformulations ⁴The toner was present as 7% of the PC Black pigmentadditive formulation ⁵The toner was present as 7% of the REACTINT ®polymeric colorant combination ⁶The toner was present as 7% of both thePC Black pigment and the REACTINT ® polymeric colorant combination priorto admixture of both formulations

These coloring agent examples were then utilized within a polyurethanefoam production method to form a finished black foam. Such polyurethanefoam articles were produced through the reaction of the followingcomponents:

TABLE 3 Polyurethane Components Component Amount (php of the polyolcontent) F3022 Polyol 100 parts Water 5.3 DABCO 33 LV (catalyst) 0.31DABCO T10 (catalyst) 0.48 L520 Silicone (from Crompton) 1.5 MethyleneChloride 5.4 82/20 toluene diisocyanate 55 Colorant Additive (from Table2) (as indicated)Upon mixture within a reaction vessel, the reaction created a “health”bubble (indicating satisfactory gelation and blowing balance), and thevessel was then exposed to 185° C. (generated within a microwave oven tosimulate actual temperatures encountered on an industrial productionlevel) for about 10 minutes. The resultant foam bun was then sliced inhalf and analyzed empirically. The jetness of the black foam was thenanalyzed for each sample.

The respective color strengths (jetness levels, etc.) of each were thenmeasured as in relation to each corresponding comparative throughanalyses of the improvements provided by such toning agents withinpolyurethane black colorants in the actual measured redness/greenness(a*) (the greater the a*, the more redness present, and thus the lowerthe a* the more greenness present), blueness/yellowness (b*) (thegreater the b* value, the more yellowness present, and thus the lowerthe b* value, the more blueness present), and lightness/darkness (L*)(lighter is a greater L* value, darker is lower) of the resultantcolorations within target polyurethane foam articles. The CIELAB (a*,b*, and L*) values were measured via a calorimeter in standard fashionfor each after foams were made therefrom as provided below.

TABLE 4 Color Measurements For Produced Polyurethane Foams Foam ExampleColoring Agent a* b* L* 202 12 0.49 0.54 25.4 203 13 0.54 −0.19 25.18204 14 0.61 −0.82 25.67 205 15 0.67 −1.72 24.7 206 16 1 −4.06 24.7 20717 0.16 −2.43 48.6 208 18 1.38 −9.79 47.54 209 19 2.61 −13.98 44.98 21020 3.71 −17.47 42.75 211 21 7.53 −24.11 36.21 212 22 0.4 0.18 24.94 21323 0.47 −0.8 24.22 214 24 0.73 −1.26 24.82 215 25 0.93 −2.03 27.18 21626 1.26 −5.29 26.04 217 27 0.35 −0.16 23.93 218 28 0.38 −0.96 24.88 21929 0.43 −1.6 23.82 220 30 0.57 −2.83 25.4 221 31 1.09 −5.9 24.33 222 320.18 0.12 25.37 223 33 −0.02 −0.1 26.23 224 34 −0.07 −0.28 26.57 225 35−0.24 −0.47 27.66 226 36 0.35 −0.6 24.65 227 37 0.25 −1.95 23.66 228 380.18 −3.56 22.59 229 39 0.11 −4.22 22.42 230 40 0.25 −0.1 25.14 231 410.14 −0.75 24.99 232 42 0.03 −2.44 24.3 233 43 −0.09 −4.07 23.31 234 44−0.13 −2.73 28.9 235 45 −0.28 −3.24 26.26 236 46 −0.69 −5.46 26.07 23747 −0.84 −7.43 25.5 238 48 −0.91 −1.82 65.8 239 49 −0.98 −2.75 45 240 50−0.86 −3.12 34.8 241 51 −0.76 −3.22 26 242 52 −0.73 −3.71 19.7 243 53−0.45 −2.54 17.5 244 54 −0.34 −1.73 16 245 55 −0.24 −0.7 64.3 246 560.09 −0.6 42.1 247 57 0.09 −0.93 32.3 248 58 −0.29 −2.01 25.3 249 59−0.26 −1.96 19.9 250 60 −0.29 −1.97 17.9 251 61 −0.39 −2.05 15.6 252 62−0.24 −0.78 63.7 253 63 −0.59 −2.14 42.4 254 64 −0.52 −2.7 32.6 255 65−1.17 −6.32 24.6 256 66 −0.48 −3.25 18.9 257 67 −0.37 −3.12 17 258 68−0.45 −3.26 15.2 259 69 −0.16 0.82 66 260 70 0.17 1.1 43.9 261 71 0.30.96 33.4 262 72 0.29 0.6 25.4 263 73 0.06 −0.17 19.6 264 74 −0.04 −0.3917.3 265 75 −0.17 −0.59 15.4 266 76 −0.16 0.82 66 267 77 0.17 1.1 44.2268 78 0.3 0.96 33.3 269 79 0.29 0.6 25.6 270 80 0.06 −0.17 18.9 271 81−0.04 −0.39 17.6 272 82 −0.17 −0.59 15.7 273 83 −1.41 −3.86 65.8 274 84−1.64 −5.78 43.8 275 85 −1.32 −5.38 33.7 276 86 −0.2 −2.33 23.8 277 87−0.49 −3.21 19.7 278 88 −0.28 −2.27 17.3 279 89 −0.31 −2.01 15.8(Comparatives) 300 100 0.27 0.24 25.15 301 101 0.1 −2.32 28.15 302 1020.01 −0.85 49.74 303 103 0.42 0.73 25.61 304 104 0.46 1.03 24.88 305 105−0.78 −0.08 67.7 306 106 −0.79 −0.46 47.2 307 107 −0.81 −1.17 38.6 308108 −0.69 −1.65 29.7 309 109 −0.3 −1.27 21.7 310 110 −0.2 −1.19 18.9 311111 −0.22 −0.97 16.6 312 112 −0.16 0.82 65.7 313 113 0.17 1.1 43.4 314114 0.3 0.96 33.2 315 115 0.29 0.6 25.5 316 116 0.06 −0.17 19.4 317 117−0.04 −0.39 17.6 318 118 −0.17 −0.59 16.5

It was thus found that in comparison with the untoned black coloringagents, the correlated toned foams exhibited lower levels of b* valuesthroughout (indicating simultaneous increase in blueness and reductionin yellowness), and each of the lower b* value foams exhibited anempirical jetter black appearance than their comparison foams with thesame or greater amounts of colorant present therein. The inventive foamsalso exhibited at least acceptable L* value levels as an indication ofacceptable jetness as well, all at lower levels of black coloring agenttherein. For example, the Comparative Example 104 (the PC Black colorantalone at a level of 2 php) L* value was comparable to or higher than theinventive Examples 12–16, and 36–39, including the toned PC Black with atotal of 2 php of both the coloring agent and the toning component).Furthermore, as another example, the L* Value of Comparative Example 101was comparable to or higher than those measured for inventive Examples44–47. Most of the inventive samples also exhibited lower a* values incomparison with the corresponding non-toned examples as well. As such,throughout the examples, it is evident that through the mere addition oflow levels of toning agent, jetter black polyurethane foams may beproduced with reduced amounts of black coloring agent present, or, atthe very least, comparable jet-black results are possible with suchlower levels of black colorant present. The same results are noticeablewith the polymeric colorant combinations (with from 20–30% improvementsat like amounts of colorant present).

Such unexpected results may also be analyzed by producing build curvesfor certain toned and untoned examples in specific 1.5 pcf densitypolyether foam (made in accordance with the formula of Table 3, above)(in terms of L* value modifications with added toner amounts present).For the following tables, A indicates PC Black alone, B indicates PCBlack with 5% of #5 from Table 1 added, C indicates PC Black with 7% of#5 from Table 1 added, D indicates REACTINT® X77 alone, E indicatesREACTINT® X77 with 5% of #5 from Table 1 added, and F indicatesREACTINT® X77 with 7% #5 from Table 1 added. The L* Value results forsuch examples with different additive loadings are tabulated below:

TABLE 5 L* Values of Black Polyether Foam (Pigment) Loading of TotalPigment plus any Toner A (L* Value) B (L* Value) C (L* Value) 0.1 php62.9 62.1 61.2 0.5 php 43.1 41 39.4   1 php 33.5 31.1 31.1   2 php 25.223.1 23.9   4 php 20.3 18.4 19.4   6 php 18.4 16.8 17.2  10 php 17.115.6 15.4  15 php 16 14.5 14

The results are provided graphically within FIG. 1, thereby showing theability to provide jetter black results with lower amounts of actualblack coloring agent present.

TABLE 6 L* Values of Black Polyether Foam (Polymeric Colorants) Loadingof Total Polymeric Colorant plus Toner D (L* Value) E (L* Value) F (L*Value) 0.1 php 69.9 66.7 66 0.5 php 50.7 45.8 45   1 php 40.3 36.2 34.6  2 php 29.4 26.2 26   4 php 22.6 19.7 20   6 php 21 17.3 18  10 php20.2 15.8 15.8  15 php 19 15 14.5

The results are provided graphically within FIG. 2, thereby showing theability to provide jetter black results with lower amounts of actualblack polymeric colorant present.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a build curve in relation to the results tabulated for Table5, above, and thus for black pigment alone versus two different levelsof toned black pigment colorant formulations for polyether polyurethaneslabstock foam.

FIG. 2 is a build curve in relation to the results tabulated for Table6, above, and thus for black polymeric colorant combinations aloneversus two different levels of toned black polymeric colorantcombination formulations for polyether polyurethane slabstock foam.

DETAILED DESCRIPTION OF THE DRAWINGS

In FIG. 1, there is supplied the build curve for Table 5, above, showingthe modification of L* values for such black polyether foam articlesthrough the introduction of increasing amounts of toner components(bluing agents). Thus, with the loading amount of pigment or pigmentplus toner remaining static for each taken measurement along therespective curves, it is evident that the increased amount of tonertranslates, unexpectedly, into a lower L* value measurement at everymeasured point along the curves. Thus, the resultant toned black foamsexhibit jetter black appearances, even though lower amounts of blackpigment are present therein.

In FIG. 2, there is supplied the build curve for Table 6, above, showingthe modification of L* values for such black polyether foam articlesthrough the introduction of increasing amounts of toner components(bluing agents). Thus, with the loading amount of polymeric colorantcombinations or such a combination plus toner remaining static for eachtaken measurement along the respective curves, it is evident that theincreased amount of toner translates, unexpectedly, into a lower L*value measurement at every measured point along the curves. Thus, theresultant toned black foams exhibit jetter black appearances, eventhough lower amounts of black polymeric colorant combinations arepresent therein.

Thus, it is evident that the inventive combination of black coloringagents plus toner (bluing agent) provides the unexpectedly effectivejetter black results within polyurethane slabstock foam articles suchthat greater amounts of black coloring agents are required to providethe same high level of jetness possible with such novel toning/blackcoloring agent combinations for such polyurethane articles. Stated inanother way, then, the presence of a toner permits a reduction in L* andb* values for a black polyurethane slabstock foam article comprising acertain amount of black coloring agent therein as compared to the sameblack polyurethane slabstock foam article but without any toner present,although the only required reduction is in b* values to provide theperceived jet-black improvement within the target black polyurethanefoam articles.

Having described the invention in detail it is obvious that one skilledin the art will be able to make variations and modifications theretowithout departing from the scope of the present invention. Accordingly,the scope of the present invention should be determined only by theclaims appended hereto.

1. A black-colored polyurethane foam article comprising at least oneblack pigment and at least one discrete toner compound, the tonercompound comprising a triphenylmethane chromophore; wherein said tonercompound exhibits at least one absorption peak with a λ_(max) between560 and 610 nm within said article and a half-height bandwidth range offrom 40 nm to 130 nm in relation to said at least one absorption peak;and wherein the cumulative mass of said at least one toner compound isin the range of about 0.1 to not more than 6% of the cumulative mass ofsaid at least one black pigment present within the target polyurethanefoam article.
 2. The article of claim 1, wherein said at least one tonercompound exhibits a half-height bandwidth of at most 120 nm in relationto said at least one absorption peak.
 3. The article of claim 1, whereinsaid at least one black pigment is selected from the group consisting ofcarbon black, lamp black, and any mixtures and combinations thereof. 4.The article of claim 2, wherein said at least one black pigment isselected from the group consisting of carbon black, lamp black, and anymixtures and combinations thereof.
 5. The article of claim 1, whereinthe triphenylmethane chromophore conforms to the structure of Formula(II)

wherein R₅, R₆, R₇, R₈, R₉, and R₁₀ are the same or different and areselected from the group consisting of hydrogen, C₁–C₂₀ alkyl, C₁–C₂₀alkoxy, phenyl and substituted phenyl, and [polyoxyalkyleneconstituent]_(z)R′, wherein z is from 1 to 20, polyoxyalkyleneconstituent comprises at least one monomer selected from the groupconsisting of a C₂–C₂₀ alkyleneoxy group, glycidyl, or mixtures thereof,and R′ is a group selected from the group consisting of hydrogen, C₁–C₂₀alkyl, C₁–C₂₀ alkylester, halo, hydroxy, thia, cyano, sulfonyl, sulfo,sulfate, aryl, nitro, carboxyl, C₁–C₂₀ alkoxyl, amino, alkylamino,acrylamino, C₁–C₂₀ alkyithic, alkylsulfonyl, C₁–C₂₀ alkoxylcarbonyl andphenyithia; wherein X is selected from the group consisting of F, Cl,Br, I, NO₂, SO₄, HSO₄, PO₄, HPO₄, H₂PO₄, and R′SO₃ and R′ is selectedfrom the group consisting of C₁–C₂₀ alkyl, phenyl, or substitutedphenyl.